The present invention relates to copolymers for use in high-solids coating compositions.
An advantage of high-solids coating compositions is reduced emission of organic compounds when a coating material is applied. In order to obtain these high-solids coating formulations it is necessary, for example, to employ appropriate acrylate resins having low viscosities, i.e., low molar masses.
It is well known that in order to prepare low-viscosity polymers it is possible to employ free-radical solution polymerization. See EP 408 858, EP 398 387, U.S. Pat. No. 4,145,513, and WO 92/18255. The disadvantage of these processes is that the properties of the polymers are adversely affected by the use of considerable quantities of polymerization initiators and polymerization regulators, and also by the formation of secondary products, some of which are not incorporated into the polymer chain. In particular, the polymerization regulators used, for example thiols, can have a foul odor or may even be toxic.
The polymers obtained by free-radical solution polymerization at high pressure and/or at high temperature in high-boiling solvents do not have these disadvantages but, because of their very low molar masses, they frequently have glass transition temperatures which are too low to permit their use as binders for coating. This results in the coatings of these materials having dust-dry times and tack-free drying times which may be of indeterminate length. In addition, some systems have a processing time which is inadequate for commercial application.
Bulk polymerization is also known, see EP 0 027 931 and EP 0 056 971, in which one component, for example a glycidyl ester or a maleate, is the initial charge in a polymerization and can thus act as solvent. This ester or this monomer, respectively, is incorporated completely into the copolymer during the subsequent course of the polymerization with the addition of monomers (further monomers in the case of maleate). These copolymers can be used to prepare binders for high-solids coating materials.
The great advantage of bulk polymerization, in comparison to a pure mass polymerization, is in the efficient dissipation of the heat of reaction and in the free choice of the solvents for dilution once the reaction has concluded. The correct choice of the reaction parameters, in particular of the reaction temperature, then leads to products with low viscosities and a high solids content in a finished coating formulation.
However, the successive increase in the reaction temperature of the products of EP 0 027 931 and of DE-P43 24 801.2 results in products which, although having very low molar masses and consequently very low viscosities as a result, also had glass transition temperatures below room temperature (20.degree. C.) and possessed drying times which were consequently too long to permit use as coating compositions.
At very low molar masses in particular, there is a heavy dependency of the glass transition temperature on the molar mass. Attempts to predict the glass transition temperatures of these low molecular weight copolymers by the Gordon-Taylor equation (M. Gordon, J. S. Taylor, J. Appl. Chem. USSR, 2, 493, 1952) or the Fox equation (T. G. Fox, Proc. Amer. Phys. Soc. 1, 123, 1956) ended in failure. Not the least of the reasons for this is that these additivity equations for the glass transition temperature take into account only the composition of the copolymers and not the varying dependency of the glass transition temperature on the molar mass of the corresponding homopolymers and copolymers in this range.